Modification of stereoregular polyolefins with polymeric compositions



United States Patent 3,337,651 MODIFICATION OF STEREOREGULAR POLYOLE-FINS WITH POLYMERIC COMPOSITIONS Jack J. Press, 1218 E. LaureltonParkway, Teaneck, NJ. 07666 No Drawing. Filed Sept. 28, 1965, Ser. No.491,055 6 Claims. (Cl. 260-895) The invention described herein may bemanufactured and used by or for the Government of the United States ofAmerica for governmental purposes without the payment of any royaltiesthereon or therefor.

This application is a continuation-in-part of my copending applicationSerial Number 400,611, filed Sept. 30, 1964, which is acontinuation-in-part of application Serial Number 113,972, nowabandoned.

The invention relates to stereoregular polyolefins. More particularly,this invention relates to polymeric compositions having improvedafiinity for dyes, said compositions containing a major amount ofstereoregular polyolefins.

It is known that polyethylene is vastly unsuitable for the production oftextile fibers due to the relatively poor properties imparted to theproduct. For one thing, a staple polyethylene fiber will not hold acrimp and this is necessary for textile processing. For another, it isuseless to make a textured or stretched yarn from a continuouspolyethylene filament because the characteristics imparted to the yarnare not maintained during weaving, dyeing, or ordinary use. Further, thematerial from which a fabric is made must be thermally stable before itmay be subjected to ordinary use. It must not have a relatively lowmelting point, and the final fabric must not have a high degree of heatsensitivity, nor relatively soft mechanical properties at elevatedtemperatures. However, the thermal properties of a polyethylene fabricare such that it is impossible to subject it to ordinary ironing withoutphysically damaging the fabric and it has been found to shrink in theconventional dryer. As is apparent from the foregoing, polyethylenecannot be utilized in the manufacture of everyday fabrics for ordinaryuse.

In recent times, it has been found that certain linear crystallinehydrocarbon polymers containing stereoregular macromolecules and havingmelting points between 150 and 300 C. can be used for the production oftextile fibers without the inherent difliculties encountered with theuse of polyethylene polymers for this purpose. Aside from melting pointdifferences, polypropylene with a tertiary carbon and a methyl sidechain, crystallizes differently and has a much higher resilience andelasticity. These properties are essential in generally useful textilefiber. Further, polymers of olefinic hydrocarbons containingstereoregular macromolecules, such as polypropylene, polymethylpentene,and polymethylbutene, ofier considerable advantages in the production offibers, particularly because of their good mechanical properties andlight weight. However, such polymers have not been satisfactory beauseof their poor afiinity for dyes, this poor affinity being due to theparticular chemical nature of such polyolefinic hydrocarbons.

Many processes have been proposed in order to improve the affinity ofsuch polyolefinic hydrocarbons for dyes, such as the addition of solublesolid substances to the molten polyolefin before spinning. The additionof basic substances facilitates dyeing with acid dyes, whereas theaddition of acid substances favors dyeing with basic dyes.

However, such processes have not been completely satisfactory becausesoluble modifiers interfere with crystallization, impair strength andthermal stability, and are not sufiiciently available in the amorphousregions Where dyeing takes place.

It has also been proposed to increase the affinity of dyes forpolyolefin fibers by grafting monomers onto the fibers after subjectingthe fibers to a preliminary peroxidation or to high energy radiation.When such processes are applied to the polyolefin after it is. infilamentary form the surface properties of the grafted fibers areconsiderably modified and the dye receptivity is improved. However, whensuch processes are applied to highly crystalline filaments, any graftingonto the preformed fibers takes place only at the surface. Therefore,subsequent dyeing is limited to the surface portion ofthe fiber and thedye does not penetrate inside the fiber.

It is therefore an object of this invention to provide a polymericcomposition having improved affinity for dyes devoid of all thedifficulties of the prior art.

In my copending application, Serial No. 400,611, filed Sept. 30, 1964, Idescribe a class of modified stereoregular polyolefins having increasedaffinity for dyes and other polar substances comprising a matrix of astereoregular polyolefin taken from the group consisting ofpolypropylene, polymethylpentene and polymethylbutene, said matrix ofpolyolefin having dispersed therein between about 2 and 20% of amodifying polymer which is hydrophilic, non-soluble in the polyolefinand fusible at a temperature not exceeding the temperature of processingof the polyolefin C. to 350 C.), said modifying polymer be ing selectedfrom the group consisting of alkylene oxide polymers having molecularweights between 100,000 and 5,000,000; poly N-vinyl pyrrolidone; polyN-vinyl morpholine; and poly N-vinyl oxazolidinone.

However, the above heterocyclic modifiers only show poor to fairuniformity of dispersion in the stereoregular polyolefin.

This invention relates to stereoregular polyolefins, modified withchemically substituted heterocyclic polymers, having an afiinity fordyes and other polar substances to a degree at least equal to that shownin the above copending application, but with improved uniformity ofdispersion. The polymeric compositions of this invention comprise amatrix of stereoregular polyolefin taken from the group consisting ofpolypropylene, polymethylpentene, and polymethylbutene, said matrixhaving dispersed therein between 2 and 20% of a second, hydrophilic,non-soluble, fusible and partially substituted polymeric composition,said second substituted polymeric composition consisting of one of thefollowing, viz:

(a) 50 to 98 mole percent of N-vinyl methyl oxazolidinone and 2 to 50mole percent of N-vin'yl-R-oxazolidinone where R is an alkyl, aryl,alkaryl, or alko-xy group having 4 to 30 carbons;

(b) 50 to 98 mole percent of N-vinyl morpholinium and 2 to 50 molepercent of N-R quaternary N-vinyl morpholinium wherein R is an alkyl,aryl, alkaryl, or alkoxy group having 4 to 30 carbons;

(c) 50 to 98 mole percent of N-vinyl pyrrolidone and 2 to 50 molepercent of R-4-vinylamino butanamide wherein R is an alkyl, aryl oralkaiyl group having 4 to 30 carbons;

(d) 50 to 98 mole percent of N-vinyl pyrrolidone and 2 to 50 molepercent of R-4-vinylamino butanoate wherein R is an alkyl, aryl oralkaryl group having 4 to 30 carbons; and

(e) 50 to 98 mole percent of N-vinyl pyrrolidone and 2 to 50 molepercent of N-vinyl-R-oxazolidinone wherein R is an alkyl, aryl, alkarylor alkoxy group having 4 to 30 carbons.

The stereoregular polyolefins which may be used within the concept ofthis invention include isotactic and syndiotactic polyolefins. Thesematerials are usually made by utilizing stereo-specific catalysts whichgive polymers which are substantially linear and which develop a highdegree of crystallinity.

Within this concept, for improved dispersibility, 2 to 50% of themonomeric units of the heterocyclic polymer making up the secondpolymeric composition are substituted by the introduction ofsubstituents having at least one alkyl, alkaryl, aryl or alkoxy groupwith 4 to 30 carbons. There is no significant reduction in melting pointor improvement in dispersibility when less than 2% of the heterocyclicpolymer are substituted. However, if more than 5 of the heterocyclicpolymer is substituted, this will result in excessive softening of theheterocyclic polymer, increased solubility in the polymer, and the needfor increased addition of the heterocyclic polymer in order to obtainthe level of modifier needed for dyeability and printability. Excessivesolubility in the polyolefin tends for excessive sweating out andseparation of the modified polymer substituents. However, the latter material may be easily removed from the polyolefin by laundering andsolvents.

I prefer to stay below 25% level of substitution of the heterocyclicpolymer, when the substituents have 12 or more carbon atoms. This isbecause the latter type substituents have a more pronounced effect onsoftening and solubility of the material in the polyolefin. The degreeof substitution should be low enough to insure that the substitutedheterocyclic polymer remains hydrophilic and soluble or dispersible inwater or an oxygenated solvent. The substituted polymer should also benon-soluble in the polyolefin and fusible at a temperature not exceedingthe temperature of processing of the polyolefin (150 to 350 C.).

The substitution of the heterocyclic polymer may take place either priorto, during, or after polymerization of the heterocyclic polymer. Thiscan be accomplished by techniques known in the art such as substitutionon a carbon of the heterocyclic ring, quaternization of the tertiaryN-alkenyl group, or by hydrolysis of the ring amide and reaction of theliberated carboxy or amine groups with an alcohol, acid, or amine grouphaving 4 to 30 carbons. The above would include substitution on the ringcarbon of N-vinyl oxazolidinone, quaternization of N-vinyl morpholine,and partial hydrolysis of the ring amide of N-vinyl pyrrolidone andreaction of the liberated carboxy groups with fatty amines or alcohols.

The following examples will illustrate the utility of the presentcomposition:

Example I (1) Each of the polymers, substituted or not, was ground to apowder (50 to 200 mesh), mixed with a given proportion of a powdered (50to 200 mesh) commercial isotactic polypropylene (molecular weight of350,000; melting point of about 170 C.; melt flow index of 3; andisotacticity of 95%) and formed into a disc in the following manner.

(2) The powder of each sample was spread uniformly in a circularshouldered Pyrex glass dish with an inside diameter of 4 inches. Thedishes were then covered by an inner nesting circular shouldered Pyrexglass dish with a bottom outer separation rib projecting downwardlyabout 0.05 inch. The assembly weighted with a preheated 5 pound weightwas then placed in an oven at 250 C. for 6 to 15 minutes. Then theweight was removed and the assembly was placed in a refrigerator atabout 4 C. to cool. The assembly dishes were then separated to give afused disc and judged for uniformity of dispersion.

(3) The disc was then cut radially into 6 equal sections and re-fusedfour times, at which time, the disc was again judged for uniformity ofdispersion.

(4) The uniformity was rated as very poorno apparent dispersion,poor-slight dispersion, fairmoderate dispersion, good-almost completedispersion, and excellent-complete dispersion.

TABLE I The following modifier combinations were formed into discs inthe manner set forth above in an amount between 2 and 20% based on theamount of polypropylene utilized.

*Monomeric units in polymer.

The discs formed above were then judged for uniformity after one andfive fusing or molding cycles as follows:

Dispersion Uniformity Modifier Percent One Mold Cycle Five Mold 0 yelesFair-good.

0. Good. Excellent.

Do. Do. Good. Excellent.

Percent by weight of modifier in polyolefin.

Example 2 In accordance with the general procedure set forth in Example1, I prepared polypropylene discs having various modifier combinationsincorporated therein as follows:

TABLE 2 Discs:

(2A) (blank)-poly N-vinyl morpholine (2B) 75%* (2A)-25 mole percentoctyl N-vinyl morpholinium chloride (20) (2A)10 mole percent octylN-vinyl morpholinium chloride (2D) 75%* (2A)25 mole percent butylN-vinyl morpholinium sulfate (2E) 90%* (2A)10 mole percent butyl N-vinylmorpholinium sulfate Footnote at end of table.

TABLE 2-Continued *Monomeric units in polymer. The discs above were thenjudged for uniformity of dispersion after one and five molding cyclesand the re sults were set forth below:

RESULTS 2 Dispersion Uniformity Percent Modifier Modifier One Mold FiveMold Cycle Cycles 5 Fair. 20 Poor.

5 Excellent. 20 Good.

5 Excellent Do.

5 Do. Good.

5 Excellent 10 Do.

5 Do. 10 Do.

Example 3 In accordance with the general procedure set forth in Example1, I prepared polypropylene discs having various modifier combinationsincorporated therein as follows:

TABLE 3 Discs:

(3A) (blank)-100% poly N-vinyl pyrrolidone (3B) 50% (3A)-50 mole percentN-butyl 4-vinylamino butanamide (3C) 75 (3A)-25 mole percent N-butyl4-vinylamino butanamide (3D) 90% (3A)-10 mole percent N-butyl4-vinylamino butanamide (3E) 75% (3A)-25 mole percent octyl 4-vinylaminobutanoate I (3F) 90% (3A)10 mole percent octyl 4-vinylamino butanoate(3G) 98% (3A)2 mole percent octyl 4-vinylamino butanoate (3H) 90% (3A)l0mole percent lauryl 4-vinylamino butanoate (31) 98% (3A)-2 mole percentlauryl 4-vinylamino butanoate (3]) 75 (3A)-25 mole percent N-benzyl4-vinylamino butanamide (3K) 90% (3A)-10 mole percent laurylbenzyl 4-vinylamino butanamide (3L) 75% (3A)-25 mole percent N-vinyltolylpyrrolidone (3M) 90% (3A)10 mole percent N-vinyloctabenzylpyrrolidone (3N) 75% (3A)25 mole percent N-vinylbutylpyrrolidone The discs made with the modifier combinations set forthin Table 3 were then judged for uniformity of dispersion after one andfive molding cycles and the results were set forth below:

RESULTS 3 Dispersion Uniformity Percent Modifier Modifier One Mold FiveMold Cycle Cycles In all dye tests with discs prepared in accordancewith the procedures of Examples 1 to 3, the stereoregular polyolefinicdiscs modified with chemically substituted heterocyclic polymers gavemore uniform results in comparison with the discs which were onlymodified with an unsubstituted polymer.

Many alternate methods of combining my modifier combinations withpolyolefins are readily available. They may be combined during formationof the polymeric modifier or during actual polymerization of the olefin,with or without melting. They may be added to freshly polymerizedpolyolefin, which is still in solution in a suitable solvent, in thepowdered form, or as a solution in a compatible solvent, or merely as adispersion. They may be added to the polyolefin during precipitation,

washing, neutralizing or compounding of the freshly prepared polyolefinprior to drying. This may be accomplished by adding the modifier as apowder or as a solution which is a non-solvent for the polyolefin.

The modifiers combinations may also be melt mixed during processing orblending of the polymer prior to use in extension of fiber, film,coating or plastic. It may also be added as a liquid or powder to finelyground or micronized polyolefin polymers and then melt dispersed in situduring hot dip or spray coating or during spreading and heat coatingoperation. They may be incorporated in polyolefin solutions or emulsionand then applied to surfaces with or without heating.

The level of addition of the modifiers heretofore listed should bebetween 2 and 20% of the weight of the overall composition. If less than2% is utilized, significant improvement will not be achieved indyeability. If an amount greater than 20% is added to the polyolefin,many of the physical properties of the final product, such as fiber orfilm, are adversely afiectedgThese include loss of strength and a lowerresistance to repeated flexing.

Under the present concept, I prefer hydrophilic polymeric modifierswhich may be soluble to either water or an oxygenated solvent but whichare not soluble in the polyolefin. I do prefer modifiers which arefusible and can be dispersed in the polyolefin.

Prior experience with comparatively less hydrophobic fiber formingpolymers, such as polyacrylonitrile polymers and polyamides, have shownthat the use of hydrophilic, water soluble or dispersi-ble, modifiers isimpractical. Mainly, because excessive amount of the modifier areleached out in scouring and dyeing processes. Surprisingly, I have foundthat my hydrophilic polymeric modifiers, when melt dispersed in the morehydrophobic polyolefin, have good dispersion stability and are notsusceptible to leachage.

I have found that at comparatively low levels of addi tion, my modifiersconfer good dyeability on the polyolefin without the necessity forcostly and sometimes impractical post treatments.

My hydrophilic modifiers must be fusible with the polyolefin. This isnecessary for the formation of a continuous network of modifierthroughout the polyolefin in order to permit dye penetration andeflficient coordination of the dye and modifier throughout the film orfiber.

The use of a non-fusible cross-linked modifier, which results in poordispersion, is ineffectual. The required modifier network in such a casecannot be formed and the discrete, separate particles are surrounded byunmodified areas within the polyolefin matrix. As a result, dyeing islimited to the fiber surface and the dye cannot penetrate into theinterior of the fiber where it is most desired.

It is generally recognized that dyeing takes place almost entirely inthe more open and readily accessible amorphous areas. When a solublemodifier is utilized, it is usually spread throughout the amorphous andcrystalline areas of the polyolefin. As a result, the modifier in thecrystalline areas is not available for improvement in dyeability. Italso interferes with crystallization and adversely affects strength andthermal stability. However, my non-soluble, hydrophilic, polymericmodifiers are not sufficiently compatible to be a part of the moreuniform and denser crystalline areas. It appears to concentrate in themore amorphous areas where it is necessary for dyeability. It has alsobeen found that an increase in molecular weight of my modifiers, furtherreduces compatibility with stereoregular polyolefins and promotesconcentration of the modifier in the more amorphous regions where it mayimprove the dyeability of the polyolefinic matrix.

Obviously, many modifications and variations of the present inventionare possible in the light of the above teaching. For instance, themodifiers of this invention may be used to increase the opacity and theaflinity of the polyolefin for finishes. They may also be used toimprove the printable of the polyolefin, increase the adhesion of :thepolyolefin to other materials, or to reduce the overall staticpropensity of the final product. It is therefore to be understood thatwithin the scope of the appended claims, the invention may be practicedotherwise than as specifically described.

I claim:

1. A polymeric composition having improved afiinity for dyes comprising:

a matrix of stereoregular polyolefin taken from the group consisting of:polypropylene, polymethylpentene, and polymethylbutene,

said matrix having dispersed therein between 2 and 20 percent of asecond, hydrophilic, non-soluble, fusible and partially substitutedpolymeric composition,

said second polymeric composition being selected from the groupconsisting of (a) 50 to 98 mole percent of N-vinyl methyl oxazolidinoneand 2 to 50 mole percent of N-vinyl-R-oxazolidinone wherein R isselected from the group consisting of an alkyl, aryl, alkaryl or analkoxy group having 4 to 30 carbons;

(b) 50 to 98 mole percent of N-vinyl morpholinium and 2 to 50 molepercent of N-R-quaternary N- vinyl morpholinium wherein R is selectedfrom the group consisting of an alkyl, aryl, alkaryl, or an alkoxy grouphaving 4 to 30 carbons;

(c) 50 to 98 mole percent of N-vinyl pyrrolidone and 2 to 50 molepercent of R-4-vinylamino butanamide wherein R is selected from thegroup consisting of alkyl, aryl, or an alkaryl group having 4 to 30carbons;

(d) 50 to 98 mole percent of N-vinyl pyrrolidone and 2 to 50 molepercent of R-4-vinylamino butanoate wherein R is selected from the groupconsisting of an alkyl, aryl, or an alkaryl group having 4 to 30carbons; and

(e) 50 to 98 mole per-cent of N-vinyl pyrrolidone and 2 to 50 molepercent of N-vinyl-R-pyrrolidone wherein R is selected from the groupconsisting of an alkyl, aryl, alkaryl or alkoxy group having 4 to 30carbons.

2. The composition of claim 1 wherein said second partially substitutedpolymeric composition is 50 to 98 mole percent of N-vinyl methyloxazolidinone and 2 to 50 mole percent of N-vinyl-R-oxazolid-inonewherein R is selected from the group consisting of an alkyl, aryl,alkaryl or an alkoxy group having 4 to 30 carbons.

3. The composition of claim 1 wherein said second partially substitutedpolymeric composition is 50 to 98 mole percent of N-vinyl morpholiniumand 2 to 50 mole percent of N-R-quaternary N-vinyl morpholinium whereinR is selected from the group consisting of an alkyl, aryl, alkaryl, oran alkoxy group having 4 to 30 carbons.

4. The composition of claim 1 wherein said second partially substitutedpolymeric composition is 50 to 98 mole percent of N-vinyl pyrrolidoneand 2 to 50 mole percent of R-4-vinylamino butanamide wherein R isselected from the group consisting of an alkyl, aryl, or an alkarylgroup having 4 to 30 carbons.

5. The composition of claim 1 wherein said second partially substitutedpolymeric composition is 50 to 98 mole percent of N-vinyl pyrrolidoneand 2 to 50 mole percent of R-N-vinylamino butanoate wherein R isselected from the group consisting of an alkyl, aryl or an alkaryl grouphaving 4 to 30 carbons.

6. The composition of claim 1 wherein said second partially substitutedpolymeric composition is 50 to 98 mole percent of N-vinyl methylpyrrolidone and 2 to 50 mole percent of N-vinyl-R-pyrrolidone wherein Ris selected from the group consisting of an alkyl, aryl, alkaryl, oralkoxy group having 4 to 30 carbons.

No references cited.

MURRAY TILLMAN, Primary Examiner.

D. J. BREZNER, Assistant Examiner.

1. A POLYMERIC COMPOSITION HAVING IMPROVED AFFINITY FOR DYES COMPRISING:A MATRIX OF STEREOREGULAR POLYOLEFIN TAKEN FROM THE GROUP CONSISTING OF:POLYPROPYLENE, POLYMETHYLPENTENE, AND POLYMETHYLBUTENE, SAID MATRIXHAVING DISPERSED THEREIN BETWEEN 2 AND 20 PERCENT OF A SECOND,HYDROPHILIC, NON-SOLUBLE, FUSIBLE AND PARTIALLY SUBSTITUTED POLYMERICCOMPOSITION, SAID SECOND POLYMERIC COMPOSITION BEING SELECTED FROM THEGROUP CONSISTING OF: (A) 50 TO 98 MOLE PERCENT OF N-VINYLMETHYLOXAZOLIDINONE AND 2 TO 50 MOLE PERCENT OF N-VINYL-R-OXAZOLIDINONEWHEREIN R IS SELECTED FROM THE GROUP CONSISTING OF AN ALKYL, ARYL,ALKARYL OR AN ALKOXY GROUP HAVING 4 TO 30 CARBONS; (B) 50 TO 98 MOLEPERCENT OF N-VINYL MORPHOLINIUM AND 2 TO 50 MOLE PERCENT OFN-R-QUATERNARY NVINYL MORPHOLINIUM WHEREIN R IS SELECTED FROM THE GROUPCONSISTING OF AN ALKYL, ARYL, ALKARYL, OR AN ALKOXY GROUP HAVING 4 TO 30CARBONS; (C) 50 TO 98 MOLE PERCENT OF N-VINYL PYRROLIDONE AND 2 TO 50MOLE PERCENT OF R-4-VINYLAMINO BUTANAMIDE WHEREIN R IS SELECTED FROM THEGROUP CONSISTING OF ALKYL, ARYL, OR AN ALKARYL GROUP HAVING 4 TO 30CARBONS; (D) 50 TO 98 MOLE PERCENT OF N-VINYL PYRROLIDONE AND 2 TO 50MOLE PERCENT OF R-4-VINLAMINO BUTANOATE WHEREIN R IS SELECTED FROM THEGROUP CONSISTING OF AN ALKYL, ARYL, OR AN ALKARYL GROUP HAVING 4 TO 30CARBONS; AND (E) 50 TO 98 MOLE PERCENT OF N-VINYL PYRROLIDONE AND 2 TO50 MOLE PERCENT OF N-VINYL-R-PYRROLIDONE WHEREIN R IS SELECTED FROM THEGROUP CONSISTING OF AN ALKYL, ARYL, ALKARYL OR ALKOXY GROUP HAVING 4 TO30 CARBONS.